Substituted-sulfonyl glycolamide compositions



United States Patent .0

3,536,721 SUBSTITUTED-SULFONYL GLYCOLAMIDE COMPOSITIONS Stassen Y. C.Soong, Taipei, Taiwan, Byron H. Lake,

Greenville, Miss., and Don R. Baker, Pinole, Calif., assignors toStaulfer Chemical Company, New York, N.Y., a corporation of Delaware NoDrawing. Original application July 15, 1966, Ser. No. 565,418, nowPatent No. 3,399,988. Divided and this application Apr. 21, 1967, Ser.No. 655,685

Int. Cl. C07c 137/00 US. Cl. 260293.4 8 Claims ABSTRACT OF THEDISCLOSURE N-substituted sulfonyl glycolamides useful as effectiveherbicides corresponding to the formula in which R is selected from thegroup consisting of alkyl, alkenyl, haloalkenyl, haloalkyl, thiophene,phenylalkyl, naphthyl, phenyl and substituted phenyl wherein thesubstituents are selected from the group consisting of halogen, alkyland nitro; R is selected from the group consisting of hydrogen, alkyl,alkenyl, cyclic alkyl, cyclic alkenyl, phenyl, phenylalkyl, furfuryl,alkoxyalkyl and cyclic alkyl ethers; and R is selected from the groupconsisting of alkyl, alkenyl, cyclic alkyl, cyclic alkenyl, phenylalkyl,furfuryl, alkoxyalkyl and cyclic alkyl ethers. Representative compoundsare O-benzene-sulfonyl-N-isopropyl glycolamide,O-methanesulfonyl-N-n-butyl glycolamide,O-p-bromobenzenesulfonyl-N-n-butyl glycolamide,O-methanesulfonyl-N,N-diallyl glycolamide, O-i-butylsulfonyl-N,N-dial1ylglycolamide, O-i-butyl-sulfonyl-N,N-(2- ethylpentamethylene)glycolamide, O-i-butylsulfonyl N- sec-butyl glycolamide.

l RisoaooHzbN wherein R is a radical selected from the class consistingof alkyl, alkenyl, haloalkyl, haloalkenyl, phenyl, substituted phenylwherein the substituents are selected from the group consisting ofhalogen, alkyl and nitro; thiophene, phenylalkyl and naphthyl, and R andR are selected from the groups consisting of hydrogen, alkyl, alkenyl,cyclic alkyl, cyclic alkenyl, phenyl, phenylalkyl, furfuryl, alkoxyalkyland cyclic alkyl ethers. By cyclic alkyl is meant a radical such ascyclohexyl which may he attached at the R and/ or R position and, inaddition, radicals such as hexamethylene which would attach at R and Rto form a ring utilizing the N atom as a ring member. Cyclic alkylethers is meant to convey an alkyl ether in which the alkyl portions ofthe ether are attached to the N atom at the R and R positions so as toform a ring structure with the N atom.

The preferred compounds of the instant invention include compoundswherein R is an alkyl having one to twelve carbon atoms, lower alkenyl,haloalkyl having one ice to twelve carbon atoms, haloloweralkenyl, alkylsubstituted phenyls wherein the alkyl contains up to twelve carbonatoms, phenyl lower alkyl, or loweralkoxyalkyls; R is hydrogen, alkylhaving up to 8 carbon atoms, or lower alkenyl; and R is hydrogen, alkylhaving up to 8 carbon atoms, or lower alkenyl. In the foregoing the termlower is meant to imply alkyls or alkenyls containing up to andincluding 5 carbon atoms.

These new and novel compounds of the present invention may be made byreacting the appropriately substituted glycolamide and the appropriatesulfonyl chloride in the presence of an organic base such astriethylamine.

Typical examples of the method of synthesis are as follows: 3

Example 1.-O-benzenesulfonyl-N-isopropyl glycolamide To the benzene (100ml.) solution of N-isopropyl glycolamide (11.7 g., 0.10 moles) andbenzene sulfonyl chloride (12.7 ml., 0.10 moles) was added 15.2 ml. oftriethylamine at 15-20 C. over a period of five minutes with stirring.The mixture was allowed to stir for one hour at '20-32" C. The mixturewas washed with water (100 ml.), dilute hydrochloric acid (100 ml.) andwater and then dried over magnesium sulfate and evaporated in vacuo toyield 22 g. of a light yellow liquid. On standing the liquidcrystallized. This was recrystallized using nbutyl ether, washed withnbutyl ether and cyclohexane to yield 13.5 g."of crystals, M.P. 64-66 C.

Example 2.-O-methanesulfonyl-N-n-butyl glycolamide To the benzene (100ml.) solution of N-n-butyl glycolamide (13.1 g., 0.10 moles) andmethanesulfonyl chloride (7.7 ml., 0.10 moles) was added triethylamine(14- ml., 0.10 moles) at 16-23" C. over a period of twenty minutes withstirring and cooling. It was then stirred at 20- 27 C. for one hour. Themixture was washed with water (100 ml.), dilute hydrochloric acid (100ml.) and water (100 ml.) and dried over magnesium sulfate. Evaporationin vacuo yielded 17 g. of an oil which on scratching formed crystals.This was recrystallized from cyclohexanezether and washed with 50:50ether-carbon tetrachloride to yield 8 g. of a first fraction (M.P. 54-56C.) and 1 g. of a second fraction (M.P. 52-53 C.).

Analysis.Found (percent), sulfur 15.5. Calc. (percent), sulfur 15.4.

Example 3.-0-p-bromobenzenesulfonyl-N-nabutyl glycolamide To the benzene(100 ml.) solution of N-n-butyl glycolamide (6.5 g., 0.05 moles) andp-bromobenzenesulfonyl chloride (12.8 g., 0.05 moles) 'was added thetriethylamine (7 ml., 0.05 moles) in one portion at 13 C. Thetemperature was kept at 13-20 C. with stirring and cooling until theexothermicity had ceased and then at 20-25 C. for 1 hours.

The mixture was washed with water (100 ml.), dilute hydrochloric acid(100 ml.) and water. It was then dried over magnesium sulfate andevaporated in vacuo to yield a light yellow oil that soon crystallizedto yield a crystalline mass. This was recrystallized from ml. of n-butylether to yield 13 g. of product. M.P. 76-77 C.

Analysis.Found (percent), bromine 22.5; sulfur 8.98. Calc. (percent),bromine 22.8; sulfur 9.15.

Example 4.O-methanesulfonyl-N,N-di-n-propyl glycolamide To the etherml.) solution of the N,N-di-n-propyl glycolamide (15.9 g., 0.10 mole),methane sulfonyl chloride (7.7 ml., 0.10 mole) was added triethylamine(14 ml., 0.10 mole) at 15-l'8 C. over a period of 45 minutes withstirring and cooling. The mixture was stirred for forty minutes and thenwashed with water (50 ml.), dilute hydrochloric acid (50 ml.) and water(50 ml.). The ether solution was dried over magnesium sulfate andevaporated in vacuo at 80 C. (20 mm.) to yield 19.5 g. of a light yellowoil. Cooling with Dry Ice induced crystals. The crystals were washedwith n-butyl ether and cyclohexane to yield 13 g. of crystals. M.P.35-37 C.

Analysis.-Found (percent), sulfur 13.5. Calc. (percent), sulfur 13.5.

These novel compounds of the present invention have dividual rowsone-half inch deep in Santa Cruz sandy loam soil contained in compressedpaper flats 8%" by 6 /2" which are 2%" deep. Enough weed seeds areplanted to give about thirty to fifty plants of each of the selectedweed species in each flat. The flats are watered after planting and thefollowing day each flat is sprayed at a rate of 20 lbs. of the compoundunder test in 80 gallons of solution per acre. A No. 152 DeVilbissatomizer is used to spray the solution on the soil surface. Two weekslater the degree of weed control is determined by also been found topossess valuable herblcrdal properties. comparing the amount ofgermination and growth of each This herbicidal activity of the compoundsof the present weed 1n the treated flats with the weeds in severaluninvention was demonstrated by the following test. treated controlflats. In reportmg the results, the herbi- Seven weed species wereindlscrnmnately selected for cldal effect of each compound with respectto each weed testing each compound from the group conslstlng of crab 15specles was checked separately and rated from 0 to 3 (0 grass, watergrass, foxtail, wild oats, lambs-quarter, redno control, 1part1alcontrol, 2good control, 3-c0mroot pigweed, Jimson weed, field bmdweed,red oats, plete control). The sum of these ratmgs based on the mustard,annual bluegrass, dock and Indian mustard. seven weed specles employedis then called the Activity Seeds of the seven selected Weed species areplanted m 111- IndeX (A.I.) and 1s mdlcated 1n the followmg table.

u R18 0 a0 OHrCN Activity Compound R R; R index 1 p-methylphenylhydrogen i-propyl 2 2 phenyl hydrogen n-butyl 20 3 phenyl hydrogeni-propyl 20 4 methyl hydrogen n-butyl 18 5 p-bromophenyl hydrogenn-butyl 15 6 methyl hydrogen i-butyl 16 7 phenyl ethyl ethyl 21 8 methylethyl ethyl 21 9 p-bromophenyl ethyl ethyl 17 10--- 4-diehlorophenylhydrogen i-propyl 11 11-.- ethyl hydrogen n-butyl 11 12W methyl allylallyl 20 13.-- 3,4-diehlorophenyl allyl allyl 18 14.-- 3,4dichlorophenylhydrogen n-propyl 16 15--- methyl n-propyl n-propyl 21 16---p-chlorophenyl n-propyl nropyl 17 17--. p-bromophenyl n-butyl nutyl 9 18methyl hexamethylene 1g 19 p-ehlorophenyl -hexamethy1ene- 15 20... phenl hexamethylene 17 21.-- methyl 2-methyl-pentamethylene 21 22... methylpentamethylene 23.- benzyl hexamethylene 2o 24-.. benzyl-pentamethylene- 18 25 p-nitrophenyl rr-propyl n-propyl 10 26-. naphthylallyl allyl 12 p-nitrophenyl -hexamethylene 14 p-fluorophenylhexamethylene- 19 methyl i-butyl i-butyl 6 p-methylphenyl -hexamethylene20 methyl hydrogen eyelohexyl 17 p-ehlorophenyl hydrogen l-butyl 18p-nltrophenyl hydrogen i-butyl 14 p-mttophenyl hydrogen i-propyl 12p-chloroghenyl hydrogen cyelohexyl 9 p-mtrop enyl hydrogen cyclohexyl 6OFClzOClzhexamethylene- 1 methyl methyl methyl 1 methyl-3-oxa-penthylmethylene- 10 n-butyl hydrogen oyclohexyl 9 methylhydrogen isopropoxypropyl 5 phenyl hydrogen isopropoxypropyl 1CFOlzCFClallyl allyl 5 phenyl hydrogen cyclohexyl 9 CHFCEP- hydrogencyclohexyl 8 methyl -tetramethylene 17 phenyl tetramethylene- 13p-nitrophenyl -tetramethylene 13 hyl hexamethylene 15 ethyl i-butyli-butyl 7 ethyl hydrogen cyclohexyl 13 n-butyl hydrogen3,4-dichlorophenyl 5 methyl hydrogen 3,4-dichlorophenyl 5 CF2 C1CClz---hexamethylene- 14 m-mtrophenyl hexamethylene 13 p-fiuorophenylpentamethylene 9 3,4=d 1ehlorophenyl hydrogen isopropoxypropyl 43,4-d1chlorophenyl -hexamethylene- 9 2naphthy1 hexamethylene 16p-lodophenyl -hexamethylene- 13 3,4-d1chlorophenyl methyl phenyl 7methyl methyl phenyl 20 p-bormophenyl -hexamethylene 7 64--. methylethyl n-butyl 19 65-.. ethyl ethyl n-butyl 21 66--- n-butyl ethyln-butyl 20 67-.- o-nitrophenyl ethyl n-butyl 14 68.-- p-fiuorophenylethyl n-butyl 13 69-.. p-nitrophenyl ethyl n-buty. 12 70---p-chlorophenyl ethyl n-butyl 13 71--- n-hutyl methyl phenyl 16 72p-ohlorophenyl methyl phenyl 16 73 p-chlorophenyl hydrogenisopropoxypropyl 11 Activity Compound R R R index propyl hydrogensec-butyl 19 butyl hydrogen sec-butyl 18 phenyl hydrogen sec-butyl l8ethyl ethyl ethyl 18 propyl ethyl ethyl 20 methyl 3,-dimethyl-4-oxopentamethylene 18 ethyl --3,5-dimethyl-4-oxopentamethylene 18 propyl -3,fi-dimethyl--oxopentamethyleue 19 butyl 3, S-dimethyl-toxopentamethylene19 phenyl 3, 5-dimethyl-4-oxopentamethylene 18 benzyl hydrogen allyl 21benzyl allyl allyl 21 benzyl hydrogen propyl 21 benzyl hydrogen i-propyl21 benzyl phenyl ethyl 12 benzyl hydrogen l-butyl benzyl hydrogen benzyl13 benzyl -2-methyl-pentamethylene 21 benzyl 3-methyl-pentamethylene- 21benzyl 4-methyl-pentamethylene- 21 hexyl -2-methyl-pentamethylenc 16octyl -2-methyl-pentamethylene 12 hexyl hydrogen l-propyl 18 octylhydrogen l-propyl 12 hexyl hydrogen sec-butyl 16 hexyl4-methyl-pentarnethylene 14 octyl 4-methyl-pentamethylene 12 hexylhexamethy1ene 19 hexyl allyl allyl 16 dodecyl n-butyl octyl 134-dodeeylphenyl allyl allyl 12 i-butyl hydrogen t-oetyl 14 l-butyl allylallyl 19 i-butyl n-propyl n-propyl 17 l-butyl -hexamethylene- 18 i-butylhydrogen benzyl 17 i-butyl 2-ethyl-pentamethylene- 20 l-butyl hydrogeneye hexyl 18 l-butyl methyl tetrahydroiurfuryl 13 l-butyl hydrogentetrahydrofurfuryl 19 i-butyl hydrogen i-butyl 18 l-butyl hydrogens-butyl 18 -butyl hydrogen n-propyl 20 i-butyl hydrogen i-propyl 11i-butyl hydrogen methyl 8 i-bntyl pentamethylene- 19 l-butyl2-me-pentamethylene- 18 In addition to the pre-emergence herbicidalactivity indicated by the above table, the compounds of the presentinvention also exhibited excellent post-emergence herbicidal activity.

We claim:

1. A compound of the formula R: H RISOZO OHQCN wherein R is selectedfrom the group consisting of alkyl having 1 to 12 carbon atoms, alkenylhaving up to and including 5 carbon atoms, haloalkenyl having up to andincluding 5 carbon atoms, haloalkyl having 1 to 12 carbon atoms,thiophene, benzyl, toluyl, naphthyl, phenyl and substituted phenylwherein the substituents are selected from the group consisting ofhalogen, alkyl having up to 12 carbon atoms and nitro; R is selectedfrom the group consisting of hydrogen, alkyl having up to 8 carbonatoms, alkenyl having up to and including 5 carbon atoms, phenyl andfurfuryl; and R is selected from the group consisting of alkyl having upto 8 carbon atoms, alkenyl having up to and including 5 carbon atoms,cyclohexyl, benzyl, furfuryl and isopropoxy lower alkyl; and R and Rtogether are hexamethylene, pentamethylene optionally substituted withlower alkyl, 3-oxo-pentamethylene tetramethylene, A -pentalene and3,5-dimethyl-4-oXo-pentamethylene.

2. A compound as stated in claim 1 wherein R is methyl and R and R areallyl.

3. A compound as stated in claim 1 wherein R is isobutyl and R and R areallyl.

4. A compound as stated in claim 1 wherein R is isobutyl and R and Rtaken together are Z-ethyl-pentamethylene.

5. A compound as stated in claim 1 wherein R is isobutyl, R is hydrogenand R is sec-butyl.

6. A compound as stated in claim 1 wherein R is isobutyl, R is hydrogenand R is n-propyl.

7. A compound as stated in claim 1 wherein R is isobutyl, R is hydrogenand R is isopropyl.

8. A compound as stated in claim 1 wherein R is isobutyl and R and R aren-propyl.

References Cited Bull. Soc. Chim. France; 1948; pp. 995, 996, 999;Lichtenberger et al.

HENRY R. JILE'S, Primary Examiner S. D. WINTERS, Assistant Examiner US.Cl. X.R.

